Gaseous diazomethane (CH2N2) has been irradiated with femtosecond laser pulses tuned to the CNN asymmetric stretch at 2100 cm(-1) in the mid-infrared. Laser-induced fluorescence detection of (CH2)-C-1 [537 nm, (b) over tilde B-1(1)(0 16 0)<--<(a)over tilde>(1)A(1)(0 0 0)] confirms infrared (IR) multiphoton-induced scission of the C-N bond on two distinct time scales, 480+/-70 fs and 36+/-8 ps. The longer time scale is consistent with a statistical dissociation process; the shorter one is indicative of directed dissociation, which occurs more rapidly than statistical intramolecular vibrational energy redistribution because of direct coupling of the vibrational energy from the IR-excitation mode into the reaction coordinate. Anisotropy measurements demonstrate that the CH2 group bends significantly out of the molecular plane prior to the dissociation. (C) 2003 American Institute of Physics.